US3661839A

US3661839A - Heat curable glass fiber filled polyvinyl chloride compositions

Info

Publication number: US3661839A
Application number: US15874A
Authority: US
Inventors: Oskar E H Klopfer
Original assignee: Ethyl Corp
Current assignee: Ethyl Corp
Priority date: 1970-03-02
Filing date: 1970-03-02
Publication date: 1972-05-09
Anticipated expiration: 1989-05-09

Abstract

A CROSS-LINKED, HEAT STABLE, GLASS FILLED POLYVINYL HALIDE COMPOSITION AND A PROCESS FOR THE PREPARATION THEREOF. THE COMPOSITION IS PREPARED BY MIXING TOGETHER POLYVINYL HALIDE RESIN, A STABILIZER, A LUBRICANT, A CROSS-LINKABLE MONOMER, AN INHIBITOR, AND GLASS FIBERS TO FORM A DRY BLEND WHICH IS MILLED ON A HOT, TWO-ROLL MILL TO FORM A RIGID SHEET. THE SHEET IS HEAT TREATED TO INCREASE DEFLECTION TEMPERATURE.

Description

United States Patent O 3,661,839 HEAT CURABLE GLASS FIBER FILLED POLY- VINYL CHLORIDE COMPOSITIONS Oskar E. H. Klopfer, Baton Rouge, La., assignor to Ethyl Corporation, New York, N.Y. No Drawing. Filed Mar. 2, 1970, Ser. No. 15,874 Int. Cl. C08f 45/72, 47/12 U.S. Cl. 260-41 AG 4 Claims ABSTRACT OF THE DISCLOSURE BACKGROUND OF THE INVENTION This invention relates to cross-linked, glass filled polyvinyl halides and to processes for the preparation thereof.

Polyvinyl halide compositions are widely used in the manufacture of coatings, flexible films, and rigid sheet. During all processes of manufacture, the sensitivity to heat of these polymers requires special precautions to be taken. Normally, this fault is dealt with by compounding and milling the composition at the requisite temperature as quickly as possible and by incorporating in the composition a suitable stabilizing agent. Processing temperature can be reduced by increasing the plasticizer content of the composition, but this normally produces a material which may be softer and more flexible than that which is required.

Polyvinyl chloride sheeting and coatings are particularly limited in use by the undesirably low temperatures at which the composition begins to soften. Polyvinyl chloride resins are used extensively as insulation for electrical conductors and other potentially high temperature applications. However, there are a number of applications where resistance to elevated temperatures is a requirement which the thermoplastic polyvinyl chloride resins cannot satisfy. This is due to the fact that rigid polyvinyl chloride compounds begin to soften and readily deform or decompose under load usually in the range of 80 to 125 C. This is equivalent to a standard heat deflection temperature range as defined in ASTM D648-56 (1961) of from about 65 C. to 75 C. under a load of 264 pounds per square inch (18.5 kg./cm.

Many attempts have been made to effect cross-linking of polyvinyl halide resins to make the resins more resistant to high temperatures. U.S. Pat. 3,351,604 describes several of these attempts, and in turn discloses methods for this purpose. This patent describes the use of certain plasticizers in a mixture with polyvinyl halide and triallyl cyanurate, either alone or in the presence of a peroxide initiator. Curing is effected by the use of heat when peroxides are present or high-energy ionizing radiation in their absence.

U.S. Pat. 3,125,546 discloses high temperature curing of a substantially linear polymer with a minor portion of a polyfunctional allyl monomer in the presence of a free radical polymerization initiator. Some of the polymers were irradiated at a dose level of about 20 megarads in order to eifect a cure of the polymeric resins.

'One of the most important advantages to be derived from the curing of cross-linked polyvinyl chloride is a Patented May 9, 1972 "Ice substantial increase in heat stability. Heat stability is generally measured in terms of heat deflection temperature.

An object of the present invention is to increase heat stability while retaining as many as possible of the other desirable properties in the resultant cured polymer.

Irradiation methods are much more expensive in general than methods not employing irradiation such as the present invention. Accordingly, another object of the pres ent invention is to increase heat stability at the lowest possible cost.

These and related problems are solved by the present invention which is more fully described in the followin specification and claims.

SUMMARY OF THE INVENTION It has been discovered that rigid, cross-linked glass filled polyvinyl halide compositions having extremely high deflection temperatures may be prepared by heat curing polyvinyl halide compositions containing a polyvinyl halide, a cross-linked monomer, and glass without the necessity of employing peroxides in the composition or of irradiating the composition. A lubricant, a stabilizer, and an inhibitor are preferably included in the composition.

Unexpectedly it has also been discovered that the above composition may be prepared by mixing the components thereof by standard techniques and at ordinary temperatures. The resultant dry blend may be molded or milled in any desired shape. The finished product is cured by heating in a conventional oven, thus eliminating the need for special extrusion or molding equipment.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Vinyl halide resins employed in the practice of the present invention may be either the homopolymer or copolymer of a major portion of the vinyl halide with an ethylenically unsaturated monomer copolymerizable therewith. In addition, the vinyl halide resin may have grafted thereon monomers such as methacrylates, acrylom'triles, and the like. Among the polyvinyl halides suitable for the invention are polyvinyl chloride, polyvinyl fluoride, and polyvinyl bromide. The most preferred polyvinyl halide is polyvinyl chloride.

Suitable ethylenicaly unsaturated monomers copolym erizable with the vinyl halides are the alpha olefins such as ethylene, for example. A suitable vinyl chloride-ethylene copolymer contains from about 0.5 to about 12 weight percent ethylene. In addition, vinyl esters of the lower saturated aliphatic monocarboxylic acids containing up to about 6 carbon atoms are equally suitable as comonomers. Suitable among the vinyl esters are vinyl acetate, vinyl propionate, vinyl hexanoate, and the like. A particularly preferred vinyl ester is vinyl acetate.

There are many other suitable monomers copolymerizable with the vinyl halides. Included among the other suitable monomers are the vinyl alkyl ethers. The vinyl alkyl ethers useful in the present invention are vinyl cetyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Generally, the alkyl present in the vinyl other may have up to about 20 carbon atoms.

The most preferred vinyl halide resin is polyvinyl chloride. Suitable polyvinyl chloride resins may be prepared by conventional polymerization processes, such as suspension, emulsion, or bulk. A suitable polyvinyl chloride emulsion resin is EH-255 sold by Ethyl Corporation. EH-255 has a particle size distribution by weight of about 3% between microns and 88 microns, about 6% between 88 microns and 74 microns, 27% between 74 microns and 44 microns, and about 64% smaller than 44 microns in diameter.

Suspension resins are especially useful in preparing the rigid, cross-linked resins of the present invention. Suitable polyvinyl chloride suspension resins are SMF-225 and SM-l75 sold by Ethyl Corporation. SMF-225 has a particle size distribution by weight of about 2 to 5% smaller than 74 microns, about 5 to between 105 and 74 microns, about 30 to 35% between 149 and 105 microns, about 50 to 55% between 177 and 149 microns, and about 5% between 250 and 177 microns. SM-175 has a particle size distribution of about 5% between 250 and 177 microns, about 35 to 40% between 177 and 150 microns, about 40 to 45% between 150 and 105 microns, about 10 to between 105 and 74 microns and about 10% below 74 microns in diameter.

Particularly preferred polyvinyl chloride resins sold commercially are SM-250 and SM-225 suspension polyvinyl chloride resins sold by Ethyl Corporation. SM-250 and SM-225 have particle size distributions by weight of about 5% between about 246 and about 175 microns in diameter, about 50% between about 175 and about,149 microns in diameter, about 35 between about 149' and 105 microns in diameter, and about 10% between about 105 and about 74 microns in diameter.

The cross-linkable monomers suitable for use in the present invention include polyol polymethacrylates, polyallyl isocyanurates, polyallyl alkyl isocyanurates, polyallyl aromatic isocyanurates, polyallyl cyanurates, polyallyl polycarboxylates, and polyvinyl aromatics.

Typical examples of polyol polymethacrylates are tetramethylene glycol dimethacrylate, triethylene (glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, glycerol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, sorbitol hexamethacrylate, and 2,2,4-trimethyl-1,3-pentanediol dimethacrylate. The

' most preferred of these compounds is trimethylolpropane trimethacrylate.

Suitable polyallyl alkyl and aromatic isocyanurates are diallyl methyl isocyanurate, diallyl ether isocyanurate, and the like, the alkyl radical having up to about 8 carbon atoms. Diallyl phenyl isocyanurate is also suitable in the present invention. In addition to these, triallyl isocyanurate is quite satisfactory, and is one of the more preferred monomers.

Suitable polyallyl cyanuratcs are diallyl methyl cyanurate, diallyl ethyl cyanurate, diallyl propyl cyanurate, and the like, the alkyl moieties having up to about 8 carbon atoms. Diallyl phenyl cyanurate has been found to be an acceptable monomer for use in the present invention.

Advantageously, economies in practicing the invention may be realized by employing polyallyl polycarboxylate monomers either alone or in combination with the other monomers taught herein. Suitable polyallyl polycarboxylates are diallyl phthalate, diallyl sebacate, diallyl adipate, triallyl trimesate, triallyl trimelitate, tetraallyl .pyromellitate, triallyl citrate, and the like. More preferred polycarboxylates are diallyl phthalate, diallyl sebacate, and triallyl citrate. Of these, the most preferred monomer is diallyl phthalate.

The polyallyl polycarboxylate monomers are especially beneficial when used in conjunction with other monomers, such as trimethylolpropane trimethacrylate, triallyl isocyanurate, triallyl cyanurate, and the like. This conjoint use of monomers in the invention is most advantageous when-diallyl phthalate is used in mixture with a monomer such as trimethylolpropane trimethacrylate or triallyl isocyanurate. Acceptable results have been obtained using up to about 80 weight percent, based on total monomers, of the polyallyl polycarboxylate.

Other suitable monomers are polyvinyl aromatics, such as divinyl benzene, divinyl naphthalene and divinylbiphenyl, as well as certain polyacrylates, such as ethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate,

glycerol triacrylate, pentaerythritol tetraacrylate, and the like.

Generaly, the allyl and methallyl acrylates or methacrylates are equally suitable in practicing the invention. Exemplary of these monomers are methallyl acrylate, methallyl methacrylate, allyl acrylate, and allyl methacrylate.

Suitable inhibitors include hydroquinone, 2,6-ditertiarybutyl paracresol, 2,6-ditertiarybutyl phenol (and derivatives) and the like. A preferred inhibitor is monomethyl ether of hydroquinone, hereinafter referred to as MEHQ. Particularly preferred is the combination of tert-butylcatechol, hereinafter referred to as t-BC.

A heat stabilizer may be employed in preparing crosslinked compositions in accordance with the present invention to prevent dehydrohalogenation of the vinyl halide resin. Typical of the stabilizers which may be employed are stearates of lead, barium, cadmium, epoxodized linseed oil, lead phosphites, and the like. A particularly preferred stabilizer is Dyphos, a dibasic lead phosphite sold by National Lead Company.

Lubricants may also be added to the composition. Typical of the lubricants which are suitable are polyethylene wax, esters of carboxylic acids having 0:20 to 26, where C=the number of carbon atoms in the compound, calcium stearate, butyl stearate, and the like. Stearic acid is particularly preferred.

The preferred filler is glass fiber. The glass fibers are preferably about inch in length. However, the fibers may suitably range from about /s inch to about 2 inches in length. A particularly preferred length is from about /a inch to about inch. The glass fibers may be monofilaments or multifilament strands. Any of the commercially available glass fibers may be used. A particularly preferred brand of glass fiber is HR-3129, manufactured by Pittsburgh Plate Glass Company.

In addition to using the glass fibers alone, other reinforcing agents and filler materials may be employed in conjunction therewith. Typically, the glass fibers are blended in an equal amount with another reinforcing agent or filler material such as a silicate, carbonate, asbestos, carbon black or other material.

Materials that have been found to be acceptable are Cabosil (Cabot Corporation), silica of millimicron size, microspheroidal silica gel, and carbon black. In addition, there are several commercially available materials made by coating calcium carbonate with fatty acid calcium salts which have been found to be especially useful in the preent invention. When these compounds are used in the invention, it may be advantageous to employ any of several available bonding agents. A particularly good bonding agent for this purpose is 'y-aminopropyltriethoxysilane, available commercially as A-l (Union Carbide).

It is important that the various components of the cross-linked polyvinyl chloride composition be mixed together in certain proportions. The following disclosed proportions are given in parts by weight of the component per hundred parts by weight of vinyl chloride resin, which is hereinafter referred to as phr.

The composition may suitably contain from about 1 phr. to about 10 phr. of stabilizer. A particularly preferred range is from about 3 phr. to about 6 phr.

The cross-linkable monomer in the composition may suitably range from about 10 phr. to about 60 phr. A pargigullalrly preferred range is from about 20 phr. to about The inhibitor may suitably may suitably range from about 0.01 phr. to about 1 phr. A particularly preferred range is from about 0.05 phr. to about 0.3 phr.

The lubricant may suitably range from about 0.5 phr. to about 2 phr. A particularly preferred range is from about 0.5 phr. to about 1.25 phr.

The composition may contain from about 15% to about 40% of glass filler. A particularly preferred range is from about 20% to about 30%.

According to the invention, the polyvinyl halide is blended with the glass fibers and cross-linkable monomer. The ingredients may be added in any order. Any conventional blender or extruder may be used to blend the in- EXAMPLE 27 100 parts of polyvinyl chloride (SMF-225 manufactured by Ethyl Corporation), 20 parts of trimethylolpropane trimethacrylate (Rohm and Haas X-980), 0.75

redients. Typical of the suitable blenders or mixers are fhe Banbury, Hobart, Henschel, Papenmeier or Farrel. fi 3:2 gfa l g giil igii 112 1 352: Typical of the various sulitable extruders are the NRM q h i 1 p g and the Egan (Plttsllaaurgb P ate G ass HR-3l29) were rmxed togetheg The resultant resin-glass blend can be molded into semii an my mixer l mlxer was run at low spoee until the temperature inslde the chamber reached 360 F. r1g1d artlcles by m1ll1ng, extrudlng, 1n ect1on moldmg, or The mm was dischar ed from the mixer and a Sam 1e compression molding. A preferred method is to mill the was I 2 d to a Sheet more min 0 erated g resin-glass blend into a sheet. The sheet may be diced into temperature of F g composition 2 p gsz g g tbs pellets used for mlectlon moldmg vanous sion molded, and test bars consisting of strips of dimen- I! 1 VP 1 I! The preferred mill for producing fiat shapes is a twoigg g 4 i ma a: if; g g g roll mill operated at a temperature of about 380 F. The 0V6 f0 S t P 5 C a o f i 1 na mill can be run at a temperature of about 350 F. to about l es t W Y 400 F., but preferably the mill is run from about 370 F. an a Owe 0 coo room empera e to about R temperature of the heat treated samples was 96.5 C.

After the glass blend is formed into some article, the $2 6 heat treatmg the deflecnon temperature was article must be heat cured to effect cross-linking. Heat curing may be carried out in any conventional oven. A snpllar results i aclpeved h the polyvmyl ch10- suitable temperature range for heat curing is from about nde leplacad wlth a vmyl qhlonde'ethylene copolymer C. to about A preferred temperature range contaimng from about 10 we1ght percent ethylene. is from about 140 C. to about 150 C. The molded article to be heat cured may be left in the oven at the foregoing EXAMPLE 28 temperatures for about 10 to about 20 minutes, but prefer- A glass-dry blend was prepared by mixing together ably for about 15 minutes. parts of polyvinyl chloride (SMF-225 manufac- Various samples were prepared in accordance with the tured by Ethyl Corporation), 20 parts of trimethylolpresent invention. The ingredients were blended together 30 propane trimethacrylate (Rohm and Haas X-980), 0.75 and milled on a two-roll mill. The mill was run at a parts stearic acid, 0.04 parts of monomethyl ether of a temperature of about 380 F. The milled sheet was cut hydroquinone, and 41.5 parts of A inch glass fibers into test bars and heat cured at a temperature of about (Pittsburgh Plate Glass HR-3l29). The glass-dry blend C. to about C. The samples were tested for was added to the first of four zones of a horizontal deflection temperature under loadb the method set forth 35 extruder (NRM manufactured by National Rubber Y in ASTM D648-56 (1961). Th1s test measures the tem- Manufacturers). The first zone was heated to 280 F., perature at which the test bar is deflected 0.25 mm. while the second zone to 300 F., the third zone to 325 F. under constant load at 264 pounds per square inch. The and the fourth zone to 325 F. The die temperature was results of the tests on the samples are listed in Table I. 325 F. Head pressure on the extruder was 3,500-5, 500

TABLE I Trimethylol propane trimeth- Glass Inhibitor 2 Parts polyvinyl acryfiller,

Number chloride resin late parts Parts Type DT; DTz

501-225 20 41.5 .04 MEHQ 106.0 103.0 sM-225 20 41.5 .04 MEHQ 101.0 105.0 SM- 20 41.5 .04 MEHQ 82.5 94.5 SM-225 20 41.9 .06 MEHQ 74.0 96.0 SM-225 20 41.9 .04 MEHQ 87.5 117.0 SM-225 15 40.2 .03 MEHQ 90.5 113.0 SM-225 25 43.6 .05 MEHQ 85.0 110.0 SM-225 25 43.6 .03 t-BC 140.0 140.0

.05 MEHQ, SM-225 25 43.6 .03 t-BC 104.0 153.5

.05 MEHQ sM-225 25 70.4 .05 MEHQ 71.0 97.5 SM-225 20 41.0 .04 ME'HQ 87.5 117.0 Eli-255 20 41.9 .04 117.0 sM-250 20 41.9 .04 SM-225 20 42 .06 SM-225 20 42 .04 SM-225 20 42 .04 SM-25O 12.5 39.1 0.01 sM-250 19 41.3 8152 SM-250 25 43.3 0103 0.05 SM-250 19 43.3 .52 SM-250 19 41.3 0105 0.04 SMF-225 19 41.6 0.09 SMF-225 25 43.6 8.82 SMF-225 20 41.5 104 SMF-225 20 41.5 .04 SMF-225 20 41.5 .04

1 All samples contained 0.75 parts by weight stearic acid.

2 MEHQ, =monomethy1 ether of hydroquinone. t-BC=tert-Butyl cateehol.

p.s.i. The extruder was operated at 20 rpm, and the resulting strands were cut to approximately /2 inch long pellets. The pellets were milled to sheet and then compression molded. The molded composition was cut into strips of 6" x /2" x A" for exposure to heat treatment.

The test bars were heat treated in a conventional oven 7 for minutes at 145 C. Deflection temperature of the bars before heat treatment was 82 C., and after heat treatment was 97 C.

Similar results are achieved when a vinyl chloridevinyl acetate copolymer is substituted for polyvinyl chloride.

EXAMPLE 29' The procedure of Example 28 was repeated with the exception that the pellets were re-extruded through the same die and then compression molded. Deflection temperature of the composition before heat curing was 86.0 C., and after heat curing was 90.5

As can be seen from the above examples, heat curing results in a substantial increase in deflection tempertures. In addition, it can be seen that the preferred method of preparing the cross-linked polyvinyl chloride composition is by milling on a hot, two-roll mill and then compression molding prior to heat treatment.

The following Examples 30 through 32 demonstrate the effect of the amount of inhibitor upon deflection temperature. All of the compositions tested in Examples 30-32 contained 100 parts of polyvinyl chloride (SMF- 2'25 manufactured by Ethyl Corporation), parts of trirnethylolpropane trimethacrylate (Rohm andHaas X- 980), 41.5 parts of A inch glass fibers (HR-3129 manufactured by Pittsburgh Plate Glass). Additionally, .02, 200, or 300 p.p.m. of monomethyl ether of hydroquinone (manufactured by Eastman Corporation) were added to Examples 30, 31, and 32, respectively. The ingredients weremixed in a conventional mixer and milled on a two-roll mill having a roll temperature of 380 F. to a sheet. The sheet was compression molded and test bars were cut therefrom in dimensions of 6 x V2" x A". The test bars were then heat treated at 145 C. for 15 minutes. The following deflection temperatures resulted:

TABLE II It can be seen that Example 31 yields the optimum deflection temperature, thereby indicating that the amount of inhibitor is critical. Example 32 contains more inhibitor than Example 31, whereas 'Example 30 contains less inhibitor than Example 31. The deflection temperature in Examples 30 and 32 are both lower than Example 31. Thus, the optimum inhibitor level is between about 285 and 385 parts per million.

It can be seen from Table I that the highest deflection temperatures are generally obtained when t-BC inhibitor is included in the glass-dry blend. The four highest deflection temperatures were obtained from cross-linked compositions which included t-BC (see Examples 8, 9, 19, and 23). The remainder of the examplesinwhicht-BC was employed yielded deflection temperatures of at least 123 C., with the exception of Example 17, in which the quantity of trimethylolpropane trimethacrylate was approximately one-half that of the other examples employing t-BC.

The compositions of the present invention are particularly useful for manufacturing plastic articles having high temperature and strength requirements, such as extruded plastic pipe for hot water, pipe fittings and valves. Some other uses are in the manufacture of injection molded articles, such as vessels, business machine housings and components, electrical motor housings and components.

What is claimed is:

1. A process for the manufacture of rigid, cross-linked vinyl halide compositions, consisting essentially of blending together:

(a) parts by weight of a vinyl halide resin selected from the group consisting of homopolymers of vinyl halides and copolymers of a major portion of a vinyl halide with an ethylenically unsaturated monomer copolymerizable therewith;

(b) from about 10 to about '60 parts by weight of a cross-linkable monomer selected from the group consisting of polyol polymethacrylates, polyallyl isocyanurates, polyallyl alkyl isocyanurates, polyallyl aromatic isocyanurates, polyallyl cyanurates, polyallyl polycarboxylates, and polyvinyl aromatics;

(c) from about 15 to about 40 percent by weight of a glass filler;

(d) forming the blend of resin, monomer and glass into a semi-rigid article; and

(e) heating said article to a temperature of from about 125 C. to about C. for about 10 to about 20 minutes.

2. The process of claim 1 wherein said resin is polyvinyl chloride.

3. The process of claim 2 wherein said cross-linkable monomer is trimethylolpropane trimethacrylate.

4. The product produced by the process of claim 1 References Cited UNITED STATES PATENTS 3,542,661 11/1970 Klopfer et al. 260884X 3,247,289 4/1966 Sears 260-884 DONALD E. CZAJA, Primary Examiner D. J. BARRACK, Assistant Examiner US. Cl. X.R.

260--23 XA, 23.5 R, 28.5 D, 31.2 R, 41 R, 41 C, 41 A, 45.7 P, 45.95, 87.5 R, 87.5 C, 87.5 G, 92.8 A, 884